Quasi-double-star nickel and iron active sites for high-efficiency carbon dioxide electroreduction

Zhang, Ting; Xu, Han; Liu, Hong; Biset‐Peiró, Martí; Zhang, Xuan; Tan, Pingping; Tang, Pengyi; Yang, Bo; Zheng, Lirong; Morante, J.R.; Arbiol, Jordi

doi:10.1039/d1ee01592c

Cited by 57 publications

(51 citation statements)

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“…[1][2][3][4][5][6] However, the inertness of CO 2 molecule and the competitive hydrogen evolution reaction (HER) greatly limit the conversion efficiency toward the practical implementation. [7][8][9] Atomically dispersed transition metals embedded in nitrogen-doped carbon matrices (M-N-C) have recently appeared at the forefront of CO 2 RR toward CO because of their feasible preparation, optimized atomic utilization and chemical stability. [10][11][12][13][14] Based on previous studies, the four-coordinated M-N 4 moieties are considered as the main active centers in common M-N-C. [15,16] However, the high structure/electron symmetry of the M-N 4 moiety, which results from the symmetrical planar structure, makes it chemically inert to a certain extent.…”

Section: Introductionmentioning

confidence: 99%

Site‐Specific Axial Oxygen Coordinated FeN₄ Active Sites for Highly Selective Electroreduction of Carbon Dioxide

Zhang

Liu

et al. 2022

Adv Funct Materials

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Regulating the coordination environment via heteroatoms to break the symmetrical electronic structure of M-N 4 active sites provides a promising route to engineer metal-nitrogen-carbon catalysts for electrochemical CO 2 reduction reaction. However, it remains challenging to realize a site-specific introduction of heteroatoms at atomic level due to their energetically unstable nature. Here, this paper reports a facile route via using an oxygen-and nitrogen-rich metal-organic framework (MOF) (IRMOF-3) as the precursor to construct the Fe-O and Fe-N chelation, simultaneously, resulting in an atomically dispersed axial O-coordinated FeN 4 active site. Compared to the FeN 4 active sites without O coordination, the formed FeN 4 -O sites exhibit much better catalytic performance toward CO, reaching a maximum FE CO of 95% at −0.50 V versus reversible hydrogen electrode. To the best of the authors' knowledge, such performance exceeds that of the existing Fe-N-C-based catalysts derived from sole N-rich MOFs. Density functional theory calculations indicate that the axial O-coordination regulates the binding energy of intermediates in the reaction pathways, resulting in a smoother desorption of CO and increased energy for the competitive hydrogen production.

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Section: Introductionmentioning

confidence: 99%

Site‐Specific Axial Oxygen Coordinated FeN₄ Active Sites for Highly Selective Electroreduction of Carbon Dioxide

Zhang

Liu

et al. 2022

Adv Funct Materials

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“…Historical works show that regulating the electronic structure of the catalytic site, thus reducing the activation energy of the intermediate *COOH, is the key to the problem. In addition to the introduction of non‐metallic heteroatoms to regulate the electronic structure of the metal active center of the M‐N 4 site, another metal atom can be introduced to obtain a diatomic site catalysts (DASCs) to regulate the coordination environment and the electronic structure of the metal active center [34–38] . By changing the combination of the two metals in DASCs, different bonding strengths can be customized, thus obtaining different binding energy between the DASCs and intermediates of CO 2 ERR [39, 40] .…”

Section: Introductionmentioning

confidence: 99%

Design of Co‐Cu Diatomic Site Catalysts for High‐efficiency Synergistic CO₂ Electroreduction at Industrial‐level Current Density

Gao

Zhou

et al. 2022

Angewandte Chemie

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Single atom catalysts (SACs) have been widely studied in the field of CO 2 electroreduction, but industrial-level current density and near-unity product selectivity are still difficult to achieve. Herein, a diatomic site catalysts (DASCs) consisting of Co-Cu hetero-diatomic pairs is synthesized. The CoCu DASC exhibits excellent selectivity with the maximum CO Faradaic efficiency of 99.1 %. The CO selectivity can maintain above 95 % over a wide current density range from 100 mA cm À 2 to 500 mA cm À 2 . The maximum CO partial current density can reach to 483 mA cm À 2 in flow cell, far exceed industrial-level current density requirements (> 200 mA cm À 2 ). Theoretical calculation reveals that the synergistic catalysis of the Co-Cu bimetallic sites reduce the activation energy and promote the formation of intermediate *COOH. This work shows that the introduction of another metal atom into SACs can significantly affect the electronic structure and then enhance the catalytic activity of SACs.

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“…The eCO 2 RR performance on the ZnO–OH sample was first evaluated by linear sweep voltammetry in both Ar- and CO 2 -saturated electrolytes (Figure S14). A large increase in the current density observed on the ZnO–OH sample after replacement of an Ar atmosphere by CO 2 suggested that CO 2 was electrochemically reduced by the ZnO–OH sample. , Meanwhile, no obvious redox peaks were observed in the CO 2 -saturated aqueous solution, which displayed that ZnO–OH tended to react with CO 2 molecules instead of suffering from self-reduction Figure a summarizes the measured total current density for ZnO–OH, D–ZnO, and C–ZnO samples.…”

Section: Resultsmentioning

confidence: 99%

Engineering the Interfacial Microenvironment via Surface Hydroxylation to Realize the Global Optimization of Electrochemical CO₂ Reduction

Zhang

Biset‐Peiró

et al. 2022

ACS Appl. Mater. Interfaces

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The adsorption and activation of CO 2 on the electrode interface is a prerequisite and key step for electrocatalytic CO 2 reduction reaction (eCO 2 RR). Regulating the interfacial microenvironment to promote the adsorption and activation of CO 2 is thus of great significance to optimize overall conversion efficiency. Herein, a CO 2philic hydroxyl coordinated ZnO (ZnO−OH) catalyst is fabricated, for the first time, via a facile MOF-assisted method. In comparison to the commercial ZnO, the as-prepared ZnO−OH exhibits much higher selectivity toward CO at lower applied potential, reaching a Faradaic efficiency of 85% at −0.95 V versus RHE. To the best of our knowledge, such selectivity is one of the best records in ZnO-based catalysts reported till date. Density functional theory calculations reveal that the coordinated surficial −OH groups are not only favorable to interact with CO 2 molecules but also function in synergy to decrease the energy barrier of the rate-determining step and maintain a higher charge density of potential active sites as well as inhibit undesired hydrogen evolution reaction. Our results indicate that engineering the interfacial microenvironment through the introduction of CO 2 -philic groups is a promising way to achieve the global optimization of eCO 2 RR via promoting adsorption and activation of CO 2 .

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Quasi-double-star nickel and iron active sites for high-efficiency carbon dioxide electroreduction

Abstract: Although the Faraday eﬃciencies (FEs) obtained on most of the Ni based single-atom catalysts (Ni-N-C) are satisfactory (generally > 90 %) for electrochemical transfer CO2 to CO, the practical application...

Cited by 57 publications

References 57 publications

Site‐Specific Axial Oxygen Coordinated FeN₄ Active Sites for Highly Selective Electroreduction of Carbon Dioxide

Site‐Specific Axial Oxygen Coordinated FeN₄ Active Sites for Highly Selective Electroreduction of Carbon Dioxide

Design of Co‐Cu Diatomic Site Catalysts for High‐efficiency Synergistic CO₂ Electroreduction at Industrial‐level Current Density

Engineering the Interfacial Microenvironment via Surface Hydroxylation to Realize the Global Optimization of Electrochemical CO₂ Reduction

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Quasi-double-star nickel and iron active sites for high-efficiency carbon dioxide electroreduction

Abstract: Although the Faraday eﬃciencies (FEs) obtained on most of the Ni based single-atom catalysts (Ni-N-C) are satisfactory (generally > 90 %) for electrochemical transfer CO2 to CO, the practical application...

Cited by 57 publications

References 57 publications

Site‐Specific Axial Oxygen Coordinated FeN4 Active Sites for Highly Selective Electroreduction of Carbon Dioxide

Site‐Specific Axial Oxygen Coordinated FeN4 Active Sites for Highly Selective Electroreduction of Carbon Dioxide

Design of Co‐Cu Diatomic Site Catalysts for High‐efficiency Synergistic CO2 Electroreduction at Industrial‐level Current Density

Engineering the Interfacial Microenvironment via Surface Hydroxylation to Realize the Global Optimization of Electrochemical CO2 Reduction

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Site‐Specific Axial Oxygen Coordinated FeN₄ Active Sites for Highly Selective Electroreduction of Carbon Dioxide

Site‐Specific Axial Oxygen Coordinated FeN₄ Active Sites for Highly Selective Electroreduction of Carbon Dioxide

Design of Co‐Cu Diatomic Site Catalysts for High‐efficiency Synergistic CO₂ Electroreduction at Industrial‐level Current Density

Engineering the Interfacial Microenvironment via Surface Hydroxylation to Realize the Global Optimization of Electrochemical CO₂ Reduction